a. Field of the Invention
This invention relates to a method for the production of unsaturated linear polyfunctional compounds, the concrete industrial importance of which will be indicated hereafter, and of their unsaturated and saturated derivatives, starting from poly-unsaturated cyclo-olefins, of which a satisfactory availability exists and the possibility of treatment and exploitation of which have been identified by the Applicant, as also hereinafter indicated.
This invention also has as its subject matter novel products having industrial importance as defined hereafter.
More specifically, the present invention concerns a method for the production, by means of processes including steps of ozonization and then of transposition of omega-formylalkenoic acids and their unsaturated derivatives starting from cyclododecatriene, cyclododecadiene, cyclooctadiene and cyclodecadecene (in the various forms and mixtures of stereoisomeric forms), and that is to say of open-chain unsaturated polyfunctional products having concrete possibilities of widespread and immediate industrial application and themselves forming subject-matter of the present invention. The unsaturated products, in particular, have important applications as polymers or as copolymers whose specific and potential reactivity, due to the presence of double bonds, enables them to find interesting uses for the manufacture of products which in turn possess particular properties, for example textile products possessing a high degree of dyeability, additives for anti-static agents or for resins and other products, all of which is easily understandable by persons skilled in the art.
As is known, cyclododecatriene-1,5,9, and likewise cyclodecadiene and cycloottadiene, are products that are obtained by known process of cyclization of butadiene, are currently available on the market and are supplied by refineries and industries which treat and process petroliferous products. These cyclo-olefins are in general transformed by the petroleum processing industries themselves, or by the utilizer industry, into the corresponding cyclomonounsaturated product. For example, cyclododecene is obtained, which is for example notoriously utilized for the production of conventional nylon 12.
B. The Prior Art
The effective and concrete industrial utilization of starting materials which in any case entail more than one unsaturation, to obtain, with high conversions, acidic aldehydes and other open-chain unsaturated functional products (a utilization confirmed by the experimental work of the Applicants, which experimental work has demonstrated the importance and the concrete possibility of new industrial developments) is not known in the technical and patent literature of the art. Thus, at least within the limits of the Applicants' knowledge, it can be held that no known technology exists previously to the present invention.
It is in fact known that the mono-ozonization of polyunsaturated olefins is a difficult operation, and that in practice it is performed only in the experimental field, with the obtaining of unacceptably low yields.
Generally, when an olefin has several double-bonds, the ozonization is not selective and more than one double bond becomes ozonized.
In the ozonization of cyclooctotetraene, i.e. of a cycloolefin having conjugated double bonds, for example (N. A. Milas -- J. Org. Chem. 23 (1958/624)), followed by reduction with sodium disulphite, there is obtained approximately 2.2 millimoles of glyoxal (OHC-CHO) per millimole of cyclooctotetraene, which is a result that indicates that more than one double bond has reacted with the ozone.
By ozonizing in solution, either with polar solvents or with non-polar solvents or with mixtures of the same, the ozonization of more than one double bond is avoided when the double bonds are not equivalent or are sterically impeded or non-reactive with ozone (J. E. Franz. U.S. Pat. No. 3,481,954).
In some cases it proves possible to ozonize only one double-bond of a poly-unsaturated cycloolefin by using large excesses of cyclo-olefin and small amounts of ozone. In such cases, the process is clearly anti-economical since it is necessary to separate, with complicated means, small amounts of mono-ozonide from large amounts of cyclo-olefin.
In the previous publications of French patent applications No 72.05593 and No 72.05594 (corresponding to applicants' U.S. Pat. Nos. 3,856,833 and 3,868,392) there was fully described and exemplified a particular methodology for the continuous production of the ozonide of a cyclo-olefin without involvement of the well-known phenomen of superoxidation. The method is based on the principle of immediate separation of the hydroperoxide, which forms as the result of reaction of the ozonide with a reactive solvent, from the environment of ozonization, by means of the use of non-solvent for the hydroperoxide.
The present Applicants have now found that, in the case of poly-unsaturated cyclo-olefins, there is obtained a more rapid and instantaneous separation of the peroxide derivative of the ozonide if addition is made to the polar solvent, generally consisting of a carboxylic acid, an anhydride of an organic acid also. The polar solvent, the anhydride of the carboxylic acid, the non-polar solvent and the polyunsaturated olefin must be at least partially soluble one with another.
The ozonide of a poly-unsaturated cyclo-olefin represents an important intermediate for the preparation of unsaturated polyfunctional compounds. This conversion is effected with yields which exceed 90%, by means of re-arrangement of the ozonide at low temperature.
The reaction is catalyzed by the combination of the anhydride of a carboxylic acid and of the alkaline salt of a carboxylic acid. Both the low temperature and the catalytic system reported are essential for the purposes of obtaining from the ozonide of a cycloolefin a single derived product and not mixtures of products.
It is in fact known (U.S. Pat. No. 2,891,988 in the name of Brokmann) that by heating the ozonides, even in the presence of reducing agents and of water, there are obtained more or less complexed mixtures of different compounds, which, in particular, are difficult to separate.
Both the potential and concrete properties of the novel method characteristic of the present invention, which method in its broadest aspect is manifested in the treatment of a cycloolefinic starting product having more than one unsaturation, and in the formation of unsaturated intermediates and/or derivatives and/or end-products, in themselves forming subject matter of the invention and which are obtained always conserving at least one unsaturation, can be expressed initially by the following principal advantages:
-- the starting unsaturated cycloolefins, such as cyclododecatriene and cyclooctadiene as available on the market, can be considered high-purity products. Even in the case of cyclododecatriene, which is in practice a mixture of its various stereoisomeric forms, the product cannot for such reason be considered impure, in view of the practically identical behaviour of these stereoisomeric forms in the subsequent treatments and conversions (ascertained by the Applicants), even though they lead to physico-chemical diversities in the unsaturated end-products, which fact in its turn represents an advantage in that it makes possible the selective obtaining of unsaturated compounds having different properties. PA0 -- in the case of production of unsaturated aminoacids, the said unsaturated end-products (in the case in point 12-aminododecadienoic -10-aminodecenoic and 8-amino-octenoic acids), when subjected to saturation processes, in particular hydrogenation, for the obtaining of the corresponding saturated aminoacids, always lead to saturated end-products having identical characteristics and properties, which are thus perfectly suitable for the subsequent processings or industrial productions foreseen.
These apprehensions, findings and the said experimental confirmation of the Applicants are, together, of great importance, particularly with respect to the aforementioned known art (which is currently held to be the only one with concrete industrial applications), according to which the product of cyclization of butadiene is first given treatments of selective or controlled hydrogenation to obtain its conversion into mono-unsaturated cycloolefin.
In fact, for example in the case of cyclododecatriene, in such conversion, in addition to cyclododecene (even though in prevalent quantity) there are also formed cyclododecane and cyclododecadiene. The said secondary fractions are among other things a cause of low industrial efficiency, in that they correspond to amounts which cannot be converted into the end products. The separation of these secondary fractions is generally intricate, costly, and sometimes incomplete. Moreover, it is known that these initial methods of conversion of the starting polyunsaturated cycloolefin, and that is to say the processes of selective hydrogenation, are, in their turn, extremely expensive. This initial selective hydrogenation, which is considered indispensable according to the present methods should in particular be compared with the method characteristic of this invention, when it is supplemented, as outlined above, by the conversion of the unsaturated aminoacid, specifically of the 12-aminododecadiene-oic acid, or the 12-aminododecenoic acid, or their admixtures, into the corresponding saturated aminoacid, inasmuch as the latter conversion does not require any special care or expedient.